1-halovinylazoles and fungicides containing them

ABSTRACT

1-Halovinylazoles of the general formula ##STR1## where A and R are identical or different and are each phenyl, biphenyl, naphthyl or hetaryl, and these radicals are substituted or unsubstituted, 
     D is chlorine or bromine, 
     X is CH or N, 
     and their plant-tolerated acid addition salts and metal complexes, and fungicides containing these compounds.

The present invention relates to novel azole compounds, processes fortheir preparation and fungicides containing them.

It is known that1-(1,2,4-triazol-1-yl)-2-(2-chlorophenyl)-2-(4-fluorophenyl)-ethene(European Patent 47057) can be used as a fungicide. However, thefungicidal actions are not satisfactory in all cases.

We have found that 1-halovinylazoles of the general formula I ##STR2##where A and R are identical or different and are each phenyl, biphenyl,naphthyl or hetaryl, and these radicals may be monosubstituted totrisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy orhaloalkyl, each of 1 to 4 carbon atoms,

D is chlorine or bromine and

X is CH or N,

and their plant-tolerated acid addition salts or metal complexes have abetter fungicidal action than known azole compounds.

The compounds of the formula I contain a polysubstituted double bond andcan therefore occur as E/Z isomers. In the case of the novel compounds,the E/Z isomers can be separated in a conventional manner, for exampleon the basis of their different solubilities or by columnchromatography, and the isomers can be isolated in pure form.

Both the individual diastereomers and the mixtures thereof can be usedas fungicidal active ingredients.

A and R are identical or different and are each, for example,1-naphthyl, 2-naphthyl, p-biphenyl, phenyl, halophenyl, 2-chlorophenyl,2-fluorophenyl, 2-bromophenyl, 3-chlorophenyl, 3-bromophenyl,3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl,2,4-dichlorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophenyl,2,6-dichlorophenyl, 2-chloro-6-fluorophenyl, C₁ -C₄ -alkoxyphenyl,2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl,C₁ -C₄ -alkylphenyl, 4ethylphenyl, 4-isopropylphenyl,4-tert-butylphenyl, 4-tertbutoxyphenyl, 2-chloro-4-fluorophenyl,2-chloro-6-methylphenyl, 3,4-dimethoxyphenyl, 3-phenoxyphenyl,4-phenoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, 3-aminophenyl,4-aminophenyl, halo-C₁ -C₄ -alkylphenyl, 2-trifluoromethylphenyl,3-trifluoromethylphenyl, 4-trifluoromethylphenyl, pyridyl, 3-pyridyl,furyl, 2-furyl, thienyl, 2-thienyl, 3-thienyl, isoxazolyl or5-isoxazolyl.

Acid addition salts are, for example, the hydrochlorides, bromides,sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates.The activity of the salts is due to the cation, so that the anion is ingeneral unimportant. The active ingredient salts are prepared byreacting the 1-halovinylazoles (I) with the acids.

Metal complexes of the active ingredients I or of their salts can beformed with, for example, copper, zinc, tin, manganese, iron, cobalt ornickel, by reacting the 1-halovinylazoles with the metal salts.

The compounds of the formula I can be prepared by reacting a compound ofthe formula II ##STR3## where A, R, D and X have the abovementionedmeanings, with a base.

The reaction is carried out in the presence or absence of a solvent ordiluent, with the addition of an inorganic or organic base, at from 10°to 120° C.

The preferred solvents and diluents include ketones, such as acetone,methyl ethyl ketone or cyclohexanone, nitriles, such as acetonitrile orpropionitrile, alcohols, such as methanol, ethanol, isopropanol,n-butanol or glycol, ethers, such as tetrahydrofuran, diethyl ether,dimethoxyethane, dioxane or diisopropyl ether, amides, such asdimethylformamide, dimethylacetamide or N-methylpyrrolidone, sulfolaneand corresponding mixtures.

The reaction is carried out in general at from 20° to 150° C. underatmospheric or superatmospheric pressure, continuously or batchwise.

The starting compounds II can be prepared, for example, by reacting acompound of the formula III ##STR4## where A, R and D have theabovementioned meanings, with a compound of the formula IV ##STR5##where X has the abovementioned meanings, in the presence of a thionylhalide (SOD₂).

The reaction is carried out in the presence or absence of a solvent ordiluent at from -30° to 80° C. The preferred solvents and diluentsinclude nitriles, such as acetonitrile or propionitrile, ethers, such astetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or diisopropylether, and in particular hydrocarbons and chlorohydrocarbons, such aspentane, hexane, toluene, methylene chloride, chloroform, carbontetrachloride or dichloroethane, and corresponding mixtures.

The compounds of the formula II can furthermore be prepared by reactinga compound of the formula V ##STR6## where A, R and X have theabovementioned meanings, with chlorine or bromine in the presence of aLewis acid, e.g. zinc chloride or zinc bromide.

The reaction is carried out in the presence or absence of a solvent ordiluent at from -30° to 100° C. The preferred solvents include esters,such as ethyl acetate, methyl acetate or butyl acetate, ethers, such astetrahydrofuran, diethyl ether, dimethoxyethane, dioxane or diisopropylether, and in particular hydrocarbons and chlorocarbons, such aspentane, hexane, toluene, methylene chloride, chloroform, carbontetrachloride or dichloroethane, and corresponding mixtures.

Preferred Lewis acids are metal halides, such as zinc chloride, zincbromide, tin chloride, tin bromide, iron tribromide, aluminumtrichloride and titaniun tetrachloride.

The compounds of the formula V can be prepared by known processes (cf.European Patents 60,223 and 47,057).

The Examples which follow illustrate the preparation of the activeingredients.

I. Preparation of the starting materials Method 11,2-Dichloro-1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethane

1.1 g of zinc chloride are added to a solution of 22.4 g of1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethene in80 ml of carbon tetrachloride, after which 8.4 g of chlorine are passedin in the form of a gas. After the reaction mixture has been stirred fortwo hours at room temperature (20° C.), the resulting precipitate isfiltered off under suction and taken up in methylene chloride, and thesolution is washed several times with saturated sodium bicarbonatesolution, dried over sodium sulfate and evaporated down. 17.8 g (63%) of1,2-dichloro-1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethaneare obtained as a 1:1 diastereomer mixture.

II. Preparation of the end products PREPARATION EXAMPLE 11-Chloro-1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethene(compound No. 1)

5.4 g of sodium methylate are added to a solution of 17.8 g (0.0503 mol)of1,2-dichloro-1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethanein 125 ml of methanol. After the reaction mixture has been refluxed forone hour, 100 ml of water are added to the solution, which is thenextracted several times by shaking with methyl tert-butyl ether. Theorganic phase isolated is washed twice with water, dried over sodiumsulfate and evaporated down, 15.5 g (97%) of1-chloro-1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)-ethanebeing obtained as a 1:1 E/Z mixture.

The compounds listed in the Table can be prepared similarly to Example1.

                                      TABLE                                       __________________________________________________________________________    Ex.                                                                              A       R         D X  m.p./IR    Isomer                                   __________________________________________________________________________     1 4-F--C.sub.6 H.sub.4                                                                  2-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N  1603, 1508, 1276, 1233,                                                                  E/Z = 1:1                                                          759 cm.sup.-1                                        2 4-F--C.sub.6 H.sub.4                                                                  2-F--C.sub.6 H.sub.4                                                                    Cl                                                                              CH                                                      3 4-F--C.sub.6 H.sub.4                                                                  2-F--C.sub.6 H.sub.4                                                                    Br                                                                              N  resin      E/Z = 1:1                                 4 4-F--C.sub.6 H.sub.4                                                                  2-F--C.sub.6 H.sub.4                                                                    Br                                                                              CH                                                      5 4-F--C.sub.6 H.sub.4                                                                  3-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N                                                       6 4-F--C.sub.6 H.sub.4                                                                  4-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N  122-125° C.                                                                       --                                        7 4-F--C.sub.6 H.sub.4                                                                  4-F--C.sub.6 H.sub.4                                                                    Cl                                                                              CH                                                      8 4-F--C.sub.6 H.sub.4                                                                  4-F--C.sub.6 H.sub.4                                                                    Br                                                                              N                                                       9 4-F--C.sub.6 H.sub.4                                                                  4-F--C.sub.6 H.sub.4                                                                    Br                                                                              CH                                                     10 4-F--C.sub.6 H.sub.4                                                                  C.sub.6 H.sub.5                                                                         Cl                                                                              N  1604, 1507, 1270, 1231                                                                   E/Z = 1:1                                                          1132, 846, 699 cm.sup.-1                            11 4-F--C.sub.6 H.sub.4                                                                  C.sub.6 H.sub.5                                                                         Br                                                                              N                                                      12 4-F--C.sub.6 H.sub.4                                                                  C.sub.6 H.sub.5                                                                         Cl                                                                              CH                                                     13 4-F--C.sub.6 H.sub.4                                                                  2-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N  1602, 1507, 1276, 1234                                                                   E/Z = 1:1                                                          753 cm.sup.-1                                       14 4-F--C.sub.6 H.sub.4                                                                  2-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              CH                                                     15 4-F--C.sub.6 H.sub.4                                                                  2-Cl--C.sub.6 H.sub.4                                                                   Br                                                                              N                                                      16 4-F--C.sub.6 H.sub.4                                                                  2-Cl--C.sub.6 H.sub.4                                                                   Br                                                                              CH                                                     17 4-F--C.sub.6 H.sub.4                                                                  3-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      18 4-F--C.sub.6 H.sub.4                                                                  4-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      19 4-F--C.sub.6 H.sub.4                                                                  4-Cl--C.sub.6 H.sub.4                                                                   Br                                                                              N                                                      20 4-F--C.sub.6 H.sub.4                                                                  4-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              CH                                                     21 4-F--C.sub.6 H.sub.4                                                                  2-Br--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      22 4-F--C.sub.6 H.sub.4                                                                  p-biphenyl                                                                              Cl                                                                              N                                                      23 4-F--C.sub.6 H.sub.4                                                                  2-naphthyl                                                                              Cl                                                                              N                                                      24 4-F--C.sub.6 H.sub.4                                                                  1-naphthyl                                                                              Cl                                                                              N                                                      25 4-F--C.sub.6 H.sub.4                                                                  2-CH.sub. 3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      26 4-F--C.sub.6 H.sub.4                                                                  2-CH.sub.3 --C.sub.6 H.sub.4                                                            Br                                                                              N                                                      27 4-F--C.sub.6 H.sub.4                                                                  2-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              CH                                                     28 4-F--C.sub.6 H.sub.4                                                                  4-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      29 4-F--C.sub.6 H.sub.4                                                                  2,4-di-CH.sub.3 --C.sub.6 H.sub.3                                                       Cl                                                                              N                                                      30 4-F--C.sub.6 H.sub.4                                                                  2-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      31 4-F--C.sub.6 H.sub.4                                                                  2-CF.sub.3 --C.sub.6 H.sub.4                                                            Br                                                                              N                                                      32 4-F--C.sub.6 H.sub.4                                                                  2-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              CH                                                     33 4-F--C.sub.6 H.sub.4                                                                  3-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      34 4-F--C.sub.6 H.sub.4                                                                  4-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      35 4-F--C.sub.6 H.sub.4                                                                  4-CF.sub.3 --C.sub.6 H.sub.4                                                            Br                                                                              N                                                      36 4-F--C.sub.6 H.sub.4                                                                  4-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              CH                                                     37 4-F--C.sub.6 H.sub.4                                                                  3-NO.sub.2 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      38 4-F--C.sub.6 H.sub.4                                                                  3-NH.sub.2 --C.sub.6 H.sub. 4                                                           Cl                                                                              N                                                      39 4-F--C.sub.6 H.sub.4                                                                  2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      40 4-F--C.sub.6 H.sub.4                                                                  2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Br                                                                              N                                                      41 4-F--C.sub.6 H.sub.4                                                                  2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              CH                                                     42 4-F--C.sub.6 H.sub.4                                                                  3-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      43 4-F--C.sub.6 H.sub.4                                                                  3-OCH.sub.3 --C.sub.6 H.sub.4                                                           Br                                                                              N                                                      44 4-F--C.sub.6 H.sub.4                                                                  4-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      45 4-F--C.sub.6 H.sub.4                                                                  4-OCH.sub.3 --C.sub.6 H.sub.4                                                           Br                                                                              N                                                      46 4-F--C.sub.6 H.sub.4                                                                  4-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              CH                                                     47 4-F--C.sub.6 H.sub.4                                                                  2-pyridyl Cl                                                                              N                                                      48 4-F--C.sub.6 H.sub.4                                                                  3-pyridyl Cl                                                                              N                                                      49 4-F--C.sub.6 H.sub.4                                                                  4-pyridyl Cl                                                                              N                                                      50 4-F--C.sub.6 H.sub.4                                                                  2-thienyl Cl                                                                              N                                                      51 4-F--C.sub.6 H.sub.4                                                                  3-thienyl Cl                                                                              N                                                      52 4-F--C.sub.6 H.sub.4                                                                  2-furyl   Cl                                                                              N                                                      53 4-F--C.sub.6 H.sub.4                                                                  5-isoxazolyl                                                                            Cl                                                                              N                                                      54 C.sub.6 H.sub.5                                                                       2-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N                                                      55 C.sub. 6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                         Cl                                                                              N                                                      56 C.sub.6 H.sub.5                                                                       2-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N  1502, 1402, 1275,                                                                        E/Z = 1:1                                                          1132, 857, 756,                                                               699 cm.sup.-1                                       57 C.sub.6 H.sub.5                                                                       4-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N  resin      E/Z = 1:1                                58 C.sub.6 H.sub.5                                                                       2-Br--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      59 C.sub.6 H.sub.5                                                                       4-Br--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      60 C.sub.6 H.sub.5                                                                       2-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      61 C.sub.6 H.sub.5                                                                       4-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      62 C.sub.6 H.sub.5                                                                       4-tert.-C.sub.4 H.sub.9 --C.sub.6 H.sub.4                                               Cl                                                                              N                                                      63 C.sub.6 H.sub.5                                                                       2-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      64 C.sub.6 H.sub.5                                                                       4-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      65 C.sub.6 H.sub.5                                                                       2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      66 C.sub.6 H.sub.5                                                                       4-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      67 C.sub.6 H.sub.5                                                                       2-naphthyl                                                                              Cl                                                                              N                                                      68 C.sub.6 H.sub.5                                                                       2-pyridyl Cl                                                                              N                                                      69 C.sub.6 H.sub.5                                                                       3-pyridyl Cl                                                                              N                                                      70 C.sub.6 H.sub.5                                                                       2-thienyl Cl                                                                              N                                                      71 C.sub.6 H.sub.5                                                                       3-thienyl Cl                                                                              N                                                      72 4-Cl--C.sub.6 H.sub.4                                                                 2-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N                                                      73 4-Cl--C.sub.6 H.sub.4                                                                 2-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      74 4-Cl--C.sub.6 H.sub.4                                                                 4-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N  1598, 1491, 1275, 1092,                                                                  --                                                                 1015, 795, cm.sup.-1                                75 4-Cl--C.sub.6 H.sub.4                                                                 2-Br--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      76 4-Cl--C.sub.6 H.sub.4                                                                 4-Br--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      77 4-Cl--C.sub.6 H.sub.4                                                                 2-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      78 4-Cl--C.sub.6 H.sub.4                                                                 4-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      79 4-Cl--C.sub.6 H.sub.4                                                                 2-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      80 4-Cl--C.sub.6 H.sub.4                                                                 4-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      81 4-Cl--C.sub.6 H.sub.4                                                                 2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      82 4-Cl--C.sub.6 H.sub.4                                                                 4-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      83 4-Br--C.sub. 6 H.sub.4                                                                2-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N                                                      84 4-Br--C.sub.6 H.sub.4                                                                 2-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      85 4-Br--C.sub.6 H.sub.4                                                                 2-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      86 4-Br--C.sub.6 H.sub.4                                                                 2-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      87 4-Br--C.sub.6 H.sub.4                                                                 4-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      88 4-Br--C.sub.6 H.sub.4                                                                 2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      89 4-Br--C.sub.6 H.sub.4                                                                 4-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      90 4-CH.sub.3 --C.sub.6 H.sub.4                                                          2-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      91 4-CH.sub.3 --C.sub.6 H.sub.4                                                          2-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N                                                      92 4-CH.sub.3 --C.sub.6 H.sub.4                                                          2-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      93 4-CH.sub.3 --C.sub.6 H.sub.4                                                          4-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      94 4-CH.sub.3 --C.sub.6 H.sub.4                                                          2-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      95 4-CH.sub.3 --C.sub.6 H.sub.4                                                          4-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      96 4-CH.sub.3 -- C.sub.6 H.sub.4                                                         2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      97 4-CH.sub.3 --C.sub.6 H.sub.4                                                          4-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      98 4-CF.sub.3 --C.sub.6 H.sub.4                                                          2-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      99 4-CF.sub.3 --C.sub.6 H.sub.4                                                          2-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N                                                      100                                                                              4-CF.sub.3 --C.sub.6 H.sub.4                                                          2-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      101                                                                              4-CF.sub.3 --C.sub.6 H.sub.4                                                          2-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      102                                                                              4-CF.sub.3 --C.sub.6 H.sub.4                                                          2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      103                                                                              4-OCH.sub.3 --C.sub.6 H.sub.4                                                         2-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      104                                                                              4-OCH.sub.3 --C.sub.6 H.sub.4                                                         2-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N                                                      105                                                                              4-OCH.sub.3 --C.sub.6 H.sub.4                                                         2-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      106                                                                              4-OCH.sub.3 --C.sub.6 H.sub.4                                                         2-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      107                                                                              4-OCH.sub.3 --C.sub.6 H.sub.4                                                         2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      108                                                                              4-OCH.sub.3 --C.sub.6 H.sub.4                                                         4-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      109                                                                              2-F--C.sub.6 H.sub.4                                                                  2-Cl--C.sub.6 H.sub.4                                                                   Cl                                                                              N                                                      110                                                                              2-F--C.sub.6 H.sub.4                                                                  2-F--C.sub.6 H.sub.4                                                                    Cl                                                                              N                                                      111                                                                              2-F--C.sub.6 H.sub.4                                                                  2-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      112                                                                              2-Cl--C.sub.6 H.sub.4                                                                 2-CH.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      113                                                                              2-Cl--C.sub.6 H.sub.4                                                                 2-CF.sub.3 --C.sub.6 H.sub.4                                                            Cl                                                                              N                                                      114                                                                              2-Cl--C.sub.6 H.sub.4                                                                 2-OCH.sub.3 --C.sub.6 H.sub.4                                                           Cl                                                                              N                                                      __________________________________________________________________________

Generally speaking, the novel compounds are extremely effective on abroad spectrum of phytopathogenic fungi, in particular those from theAscomycetes and Basidiomycetes classes. Some of them have a systemicaction and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, fruit and ornamentals in horticulture and viticulture, andin vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in vegetables and fruit.

The compounds are applied by spraying or dusting the plants with theactive ingredients, or treating the seeds of the plants with the activeingredients. They may be applied before or after infection of the plantsor seeds by the fungi. Either the fungi themselves, or the plants,seeds, materials or soil to be protected against fungal attack aretreated with a fungicidally effective amount of the active ingredient.

The novel substances can be converted into conventional formulationssuch as solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application forms depend entirely on the purposes forwhich they are intended; they should at all events ensure a fine anduniform distribution of the active ingredient. The formulations areproduced in known manner, for example by extending the active ingredientwith solvents and/or carriers, with or without the use of emulsifiersand dispersants; if water is used as solvent, it is also possible toemploy other organic solvents as auxiliary solvents. Suitableauxiliaries for this purpose are solvents such as aromatics (e.g.,xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g.,crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g.,cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), andwater; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin-sulfitewaste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt % of active ingredient. The application rates arefrom 0.02 to 3 kg or more of active ingredient per hectare, depending onthe type of effect desired. The novel compounds may also be used forprotecting materials (wood), for example against Paecilomyces variotii.

When the active ingredients are used for treating seed, amounts of from0.001 to 50, and preferably from 0.01 to 10, g per kg of seed areusually employed.

The agents and the ready-to-use formulations prepared from them, such assolutions, emulsions, suspensions, powders, dusts, pastes and granules,are applied in conventional manner, for example by spraying, atomizing,dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 6 is mixed with 10 parts by weightof N-methyl-α-pyrrolidone. A mixture is obtained which is suitable forapplication in the form of very fine drops.

II. 20 parts by weight of compound no. 13 is dissolved in a mixtureconsisting of 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into water and uniformly distributing it therein, an aqueousdispersion is obtained.

III. 20 parts by weight of compound no. 6 is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into water andfinely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 13 is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanol, 65 parts by weight ofa mineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. By pouring the solution into water and uniformlydistributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 6 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 7 parts by weight of powdered silicagel, and triturated in a hammer mill. By uniformly distributing themixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 13 is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

VII. 30 parts by weight of compound no. 6 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

VIII. 40 parts by weight of compound no. 13 is intimately mixed with 10parts by weight of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater to give a stable aqueous dispersion. Dilution in water gives anaqueous dispersion.

IX. 20 parts by weight of compound no. 6 is intimately mixed with 2parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 2 parts by weightof the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil. A stable oilydispersion is obtained.

In these application forms, the agents according to the invention mayalso be present together with other active ingredients, for exampleherbicides, insecticides, growth regulators, and fungicides, and mayfurthermore be mixed and applied together with fertilizers. Admixturewith other fungicides frequently results in an increase in thefungicidal spectrum.

USE EXAMPLE The active ingredient1-(1,2,4-triazol-1-yl)-2-(2-chlorophenyl)-2-(4-fluorophenyl)-ethene (A)disclosed in EP 47,057 was used for comparison purposes Action on wheatbrown rust

Leaves of pot-grown wheat seedlings of the "Fruhgold" variety weredusted with spores of brown rust (Puccinia recondita). The pots werethen placed for 24 hours at 20° to 22° C. in a high-humidity (90-95%)chamber. During this period the spores germinated and the germ tubespenetrated the leaf tissue. The infected plants were then sprayed torunoff with aqueous liquors containing (dry basis) 80% of activeingredient and 20% of emulsifier. After the sprayed-on layer had dried,the plants were set up in the greenhouse at 20° to 22° C. and a relativehumidity of 65 to 70%. The extent of rust fungus spread on the leaveswas assessed after 8 days.

The results show that active ingredients 6 and 13, applied as 0.025 wt %spray liquors, have a better fungicidal action (94%) than prior artcomparative agent A (55%).

We claim:
 1. A compound selected from the group consisting of those ofthe formula I ##STR7## wherein A is 4-fluorophenyl and R is selectedfrom the group consisting of phenyl, substituted phenyl, biphenylyl,substituted biphenylyl, naphthyl, and substituted naphthyl, wherein thesubstituents are 1 to 3 substituents selected from the group consistingof halo, nitro, phenoxy, amino, alkyl of 1 to 4 carbon atoms, alkoxy of1 to 4 carbon atoms, and haloalkyl of 1 to 4 carbon atoms;D is selectedfrom the group consisting of chloro and bromo; and X is N; a planttolerated acid addition salt thereof, and a metal complex thereof.
 2. Afungicidal composition containing a carrier and a fungicidally effectiveamount of a compound of claim
 1. 3. A process for combatting fungiwherein the fungi or the plant materials, plant areas, plants or seedswhich are threatened by fungus attack are contacted with a fungicidallyeffective amount of a compound of claim
 1. 4. A compound of the formula##STR8## wherein A is 4-fluorophenyl and R is selected from the groupconsisting of 2-fluorophenyl, 4-fluorophenyl, and 2-chlorophenyl, D ischloro or bromo, andX is N, or a plant tolerated acid addition salt ormetal complex thereof.
 5. A compound of the formula I as set forth inclaim 1, wherein D is Cl and R is 4-fluorophenyl.
 6. A compound of theformula I as set forth in claim 1, wherein D is Cl and R is2-chlorophenyl.